KR20170084129A - Ethylene-propylheptyl(meth-)acrylate copolymers - Google Patents

Abstract

The present invention relates to copolymers formed from monomer (s) selected from (a) ethylene and (b) propylheptyl acrylate and propylheptyl-methacrylate, and optionally one or more further monomers. The copolymer is used as an oil additive for cosmetic formulations and as an oil deposition improver, especially for rinse-off formulations.

Description

Ethyl-propylheptyl (meth) acrylate copolymer {ETHYLENE-PROPYLHEPTYL (METH-) ACRYLATE COPOLYMERS}

The present invention relates to copolymers comprising ethylene and at least one propylheptyl ester of acrylic acid or methacrylic acid in copolymerized form. The copolymers are useful as oil addition agents for cosmetic formulations and as oil deposition improvers, especially for rinse-off formulations.

In cosmetic formulations, oil-soluble additives are less common than water-soluble additives.

Most water-insoluble additives are present only in dispersed form. Examples of such additives include o / w emulsion (co-) polymerizations such as styrene-butadiene copolymers (see for example US 4,009,139), polyacrylates (see, for example, US 6,132,705, US 2007/0218089) -Vinyl acetate copolymer, an acrylate-styrene-butadiene copolymer and a vinyl acetate-ethylene copolymer (see, for example, US 4,126,144, EP 1634578). This type of polymer is generally only used as an aqueous formulation and does not apply when a pure solution of oil and additive is needed because attempts to prepare solutions in oil by the drying process are costly and can lead to crosslinking to be.

Other additives may be present in pure form and may be used directly as an additive for oil-containing cosmetic formulations. Examples of such additives include polyacrylates (see, for example, US 6,664,356) and ethylene homopolymers (see, for example, US 2,628,187, US 3,215,599). However, liquid solutions of such additives in oil often exhibit poor stability.

Thus, there is a need for additives useful in oil-containing liquid cosmetic formulations that can be readily dissolved in oil, form a homogeneous liquid oil solution that is stable to phase separation and formation of inhomogeneities, and the like.

Surprisingly, it has been found that this object is achieved by the copolymers of the present invention formed from monomers comprising ethylene and branched alkyl (meth) acrylates having the properties described below.

Polymers comprising monomeric units derived from ethylene and branched acrylates are described, for example, in US 8,338,344, WO 2012/004240 and WO 2007/135038 as cooling flow enhancers and impact modifiers for fuel.

The present invention provides a copolymer formed from the following monomers:

(a) ethylene,

(b) at least one monomer selected from propylheptyl acrylate, propylheptyl methacrylate and mixtures thereof, and

(c) optionally one or more additional monomers different from (a) and (b)

here,

(i) the amount of ethylene monomer (a) is in the range of 75 wt-% to 98 wt-%, based on the total weight of the monomers forming the copolymer;

(ii) the total amount of monomers (a) + (b) is at least 90 wt-% based on the total weight of the monomers forming the copolymer;

(iii) when present, the amount by weight of the monomer (s) (c) is less than the amount by weight of the monomer (s) (b).

Unless otherwise indicated, the following general definitions apply in the context of the present invention:

C ₁ -C ₃ -alkyl is a straight or branched alkyl group of 1 to 3 carbon atoms. Examples of C ₁ -C ₃ -alkyl groups are methyl, ethyl, n-propyl and isopropyl.

C ₁ -C ₄ -alkyl is a straight or branched alkyl group of 1 to 4 carbon atoms. Examples of C ₁ -C ₄ -alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl and tert-butyl.

C ₁ -C ₉ -alkyl is a straight or branched alkyl group of 1 to 9 carbon atoms. Examples of C ₁ -C ₉ -alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert- butyl, pentyl, neopentyl, hexyl, Hexyl, nonyl, and the constitutional isomers thereof.

C ₁ -C ₂₀ -alkyl is a straight or branched alkyl group of 1 to 20 carbon atoms. Examples of C ₁ -C ₂₀ -alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert- butyl, pentyl, neopentyl, Propylhexyl, undecyl, dodecyl (for example lauryl), tridecyl, tetradecyl (for example myristyl), pentadecyl, hexa Decyl, heptadecyl, octadecyl (e.g., stearyl), nonadecyl, eicosyl, and structural isomers thereof.

C ₁ -C ₂₀ -alkoxy is a group of the formula -OR, wherein R is a straight or branched C ₁ -C ₂₀ -alkyl group as described herein. Examples of C ₁ -C ₂₀ -alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy (2- methylpropoxy) Butoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethyl Propoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, , 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 2-methylpropoxy, 1-ethyl-2-methylpropoxy, heptoxy, octoxy, 2-ethylhexoxy, nonoxy, decoxy, 2-propylheptoxy , 4-methyl-2-propylhexoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy, octadecoxy, , A structural isomer thereof, for the city and Eiko in the formula -OR.

The alkyl and alkoxy groups may be unsubstituted or substituted. The substituted alkyl and alkoxy groups may include, without limitation, hydroxyl, C ₁ -C ₄ -alkoxy, -NR ^a R ^b and carbonyl (-C (O) R ^a ) wherein R ^a and R ^b are each independently H or C ₁ -C ₄ - has one or more substituents selected from the group comprising alkyl). In the context of the present invention, the term "alkyl" preferably denotes unsubstituted alkyl and the term "alkoxy" preferably denotes unsubstituted alkoxy.

The propylheptyl methacrylate and propylheptyl acrylate monomers used in the preparation of the copolymers of the present invention typically comprise essentially pure 2-propylheptanol, or a mixture of propylheptanolisomers (typically 2-propylheptanol Produced by industrial manufacture and generally also referred to as "2-propylheptanol").

Pure 2-propylheptanol can be prepared, for example, by aldol condensation of n-valeraldehyde and subsequent hydrogenation of the resulting 2-propylheptenal, as described in US-A 2921089. In addition to the main constituent 2-propylheptanol, commercially available 2-propylheptanol is generally used as a byproduct, such as isomers of 2-propylheptanol, such as 2-propyl-4-methylhexanol, , 2-isopropyl-heptanol, 2-isopropyl-4-methylhexanol, 2-isopropyl-5-methylhexanol and / or 2-propyl-4,4-dimethyl pentanol. Other isomers of 2-propylheptanol, such as 2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methylheptanol and / or 2-ethyl-2,5-dimethylhexanol, have.

For the preparation of 2-propylheptanol, different carbohydrate sources such as 1-butene, 2-butene, raffinate I (allene still containing significant amounts of isobutene in addition to 1- and 2- Alkane / alkene mixture obtained from the C ₄ -fraction of cracker after separation of acetylene and diene) or raffinate II (raffinate by separation of isobutene containing only a small amount of residual isobutene in addition to 1- and 2-butene) Gt; I) < / RTI > can be used as the starting material. Naturally, mixtures of raffinate I and raffinate II can be used as starting materials in the preparation of 2-propylheptanol. These olefin and olefin mixtures may be hydroformylated by methods known in the art using cobalt or rhodium catalysts to convert 1-butene to a mixture of n-valeraldehyde and iso-valeraldehyde (2-methylbutanal) Where the n / iso ratio can vary over a relatively wide range depending on the catalyst and the conditions of the hydroformylation applied. For example, when a triphenylphosphine-modified homogeneous rhodium catalyst (Rh / TPP) is used, the n / iso ratio of the generally formed n- and iso-valeraldehyde ranges from 10: 1 to 20: 1 , Almost exclusively n-valeric aldehyde is modified with a phosphite ligand (for example as described in US 5,288,918 or WO 2005/028407) or a phosphoamidite ligand (for example as described in WO 02/083695) Is formed when a rhodium catalyst is used. The conversion of 2-butene by the Rh / TPP catalyst system is so slow that it can be recovered from the largest amount of 2-butene hydroformylation mixture. In contrast, the above-mentioned rhodium catalysts modified by phosphite ligands or phosphoramidite ligands permit efficient hydroformylation of 2-butene, which is predominantly formed of n-valeraldehyde. Basically, all catalyst systems cause hydroformylation of 2-methylbutanal and the catalyst of isobutene contained in the olefinic source material and also to small amounts of pseudoaldehydes.

The mixture of the C ₅ -hydroformylated product, n-valeric aldehyde or its iso-valeraldehyde, 2-methyl butanal and / or pivalic aldehyde (according to the starting material and catalyst used) Can be completely or partially separated into a single component. This allows control of the isomeric composition of the C ₁₀ -alcohol component of the ester monomer composition used in the copolymers of the present invention. Alternatively, the C ₅ -hydroformylation product can be used in the aldol condensation reaction without prior separation of the individual isomers. Aldol condensation can be carried out in the presence of a basic catalyst such as an aqueous solution of sodium hydroxide or potassium hydroxide (for example as described in EP 0366089, US 4,426,524 or US 5,434,313). When n-valeraldehyde is used, aldol condensation essentially produces 2-propylheptanal as the sole condensation product. When a mixture of C ₅ -aldehyde isomers is used, the aldol condensation produces a single condensation product of the same aldehyde molecule and an isomeric mixture of the crosslinked condensation product of the different C ₅ -aldehyde isomers. Naturally aldol condensation can be controlled by the target conversion of the individual isomers, so as to form a single aldol condensation isomer as a major or essentially single product. The product of the aldol condensation can be hydrogenated to form the corresponding alcohol or alcohol mixture using hydrogenation catalysts known in the art (e.g. those mentioned above as being useful in the hydrogenation of aldehydes). Typically, the hydrogenation is carried out after separation of the aldol condensation product (preferably by distillation) from the reaction mixture and, if desired, purification by distillation.

When the propylheptyl acrylate and propylheptyl methacrylate monomers, respectively, forming the copolymer of the invention are prepared from 2-propylheptanol and mixtures of isomers thereof (as mentioned above), 2-propylheptanol The content of the aldehyde is generally in the range of at least 50 wt-%, especially 60-98 wt-%, preferably 80-95 wt-%, particularly preferably 85-95 wt-%, based on the total weight of the isomer mixture to be.

Suitable mixtures of 2-propylheptanol and its isomers include, for example, from 60 to 98 wt-% 2-propylheptanol, from 1 to 15 wt-% 2-propyl-2-methylhexanol, from 0.01 to 20.00 wt-% 2-propyl-5-methyl-hexanol, and 0.01 to 24.00 wt-% 2-isopropylheptanol, wherein the sum of the constituents is preferably in the range of from 100 wt-%. Preferred 2-propylheptanol and mixtures of its isomers comprise 85 to 95 wt-% 2-propylheptanol, 5-12 wt-% 2-propyl-4-methylhexanol, 0.1-2.0 wt- 5-methylhexanol, and 0.01 to 1.00 wt-% 2-isopropyl-heptanol, wherein the sum of the constituents is preferably 100 wt-% based on the total weight of the isomer mixture.

The isomeric propylheptanol-isomer mixture is used in place of the pure 2-propylheptanol for the production of propylheptyl (meth) acrylate monomers for the copolymer of the present invention, and is a propyl esterified by methacrylic acid or acrylic acid The isomeric composition of the heptyl group is basically the same as the isomeric composition of the propylheptanol-isomer mixture used in the esterification reaction.

Thus, the term "propylheptanol" as used herein includes the above-mentioned 2-propylheptanol and structural isomers thereof. The term "propylheptylarylate" as used herein also includes acrylic esters of 2-propylheptanol and acrylic esters of 2-propylheptanol as mentioned above. Similarly, the term "propylheptyl methacrylate" as used herein includes methacrylic acid esters of 2-propylheptanol and methacrylic acid esters of 2-propylheptanol structure as mentioned above.

According to a particular embodiment, the monomer (s) (b) forming the copolymer of the present invention is a 2-propylheptanol ester (s) of acrylic acid and / or methacrylic acid.

According to a further specific embodiment, the monomer (b) forming the copolymer of the invention is propylheptyl acrylate, preferably 2-propylheptyl acrylate.

The copolymers of the present invention are formed from:

(a) an ethylene monomer;

(b) at least one monomer selected from the group consisting of propylheptyl acrylate, propylheptyl methacrylate, and mixtures of propylheptyl acrylate and propylheptyl methacrylate;

And optionally (c) one or more additional monomers different from (a) and (b).

The monomer (a), i.e. the ethylene monomer, constitutes 75 wt-% (i.e., weight percentage) to 98 wt-%, based on the total weight of the monomers that form the copolymer of the present invention. Preferably, the amount of monomer (a) is 78 wt-% to 97 wt-%, more preferably 79.0 wt-% to 96.5 wt-% based on the total weight of the monomers forming the copolymer of the present invention, Lt; / RTI > to about 96 wt-%.

Monomers selected from monomer (a), i.e., ethylene monomer, and monomer (b), i.e., propylheptyl acrylate, propylheptyl methacrylate and mixtures thereof, wt-% or more. Preferably, the total amount of monomers (a) and (b) is at least 91 wt-%, more preferably at least 95 wt-%, at least 97 wt-%, based on the total weight of the monomers forming the copolymer of the present invention Or 98 wt-%, especially 99 wt-% or more.

The copolymers of the present invention formed from essentially monomers (a) and (b) are specific groups of embodiments of the present invention. The term "essentially" in this context means that the copolymer contains not more than 5 wt-%, preferably not more than 3 wt-%, more preferably not more than 2 wt-% of components other than monomers (a) and (b) Especially 1 wt-% or less. For example, as a result of the preparation, a small proportion of the compound used as the modifier (chain transfer agent) will possibly be present.

When the monomer forming the copolymer of the present invention comprises a monomer other than the monomers (a) and (b), the amount by weight of the monomer (represented by the monomer (C) .

Suitable monomers (c) include, without limitation, mixtures of two or more of the following monomers:

- Monomers of the formula M1

[Wherein,

Each of R ¹ , R ² and R ³ is independently H or C ₁ -C ₄ -alkyl, preferably H or methyl, more preferably ^two of R ¹ , R ² and R ³ are each H and the other One is H or methyl, in particular, R ¹ , R ² and R ³ are each H;

R ⁴ is C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₉ -alkyl, more preferably C ₁ -C ₃ -alkyl, specifically ethyl or methyl, especially methyl;

- Monomers of Formula M2 other than propylheptyl acrylate and propylheptyl methacrylate:

[Wherein,

R ⁵ , R ⁶ and R ⁷ are each independently H or C ₁ -C ₄ -alkyl, preferably H or methyl, more preferably two of R ⁵ , R ⁶ and R ⁷ are each H and the other One is H or methyl, especially R < ⁵ >, R < ⁶ > and R < ⁷ > are each H;

R ⁸ is C ₁ -C ₂₀ -alkyl or is selected from straight and branched chain alkyl groups, preferably branched alkyl groups having 4 to 20, 6 to 20, 8 to 20, especially 9 to 20, carbon atoms;

- Monomers of formula M3

[Wherein,

R ⁹ is independently H or C ₁ -C ₄ -alkyl, preferably H or methyl, especially H;

R ¹⁰ and R ¹¹ is -C (O) R ¹³ and the other is H or C ₁ -C ₄ -alkyl;

R ¹² and R ¹³ are each independently -OH or C ₁ -C ₂₀ -alkoxy; or

R ¹² and R ¹³ together form -O- group].

Examples of monomer M1 include, but are not limited to, vinyl or propenyl esters of aliphatic C ₂ -C ₂₀ -carboxylic acids such as acetic, propionic, butyric, valeric, isovaleric, pivalic, neopentanoic, caproic, caprylic acid, pelargonic, 2-ethylhexanoic acid, Versatic acid ^TM, especially neo-nonanoic acid and neo-decanoic acid (e.g. VeoVa ^TM = vinyl ester of suberic Satkar acid), capric acid, undecanoic acid Neo, La Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid and arachic acid. Vinyl esters of the mentioned carboxylic acids are preferred, with vinyl acetate being particularly preferred.

According to a particular embodiment of the invention, the copolymer is formed from monomers (a), (b) and Ml, and the monomer M1 is preferably vinyl acetate. According to a more particular embodiment of the invention, the copolymer is formed from ethylene monomers, propylheptyl monomers and vinyl acetate monomers.

Monomer M2 is preferably acrylic acid (R ^5, R ⁶ and R ⁷ = H), methacrylic acid ^{(R 5, R 6 = H} ; R 7 = methyl), crotonic acid ^{(R 6, R 7 = H} ; R a R ⁶ = methyl), more preferably acrylic acid and methacrylic acid, in particular, esters of α, β- unsaturated carboxylic acid selected from acrylic acid; ⁵ = methyl), and isocrotonic acid ^{(R 5, R 7 = H} . Examples of monomer M2 include, but are not limited to, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, neopentyl acrylate, isopentyl acrylate, hexyl acrylate Ethylhexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, 2-propylhept- Unsaturated acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, palmitylacrylate, stearyl acrylate, nonadecyl acrylate and eicosyl acrylate; And also the corresponding esters of methacrylic acid, crotonic acid and isocrotonic acid, preferably acrylates (esters of acrylic acid).

The monomer M3 is an ethylenically unsaturated aliphatic 1,2-dicarboxylic acid (R ¹² and R ¹³ together form an -O- group), an ethylenically unsaturated aliphatic 1,2-dicarboxylic acid (R ¹² and R ¹³ = -OH) C ₁ -C ₂₀ - monoesters of ethylenically unsaturated aliphatic 1,2-dicarboxylic acid in an alcohol (one of R ¹² and R ¹³ is -OH and the other is C ₁ -C ₂₀ - alkoxy), or C ₁ - C ₂₀ - is an acid anhydride of the (alkoxy R ¹² and R ¹³ = C ₁ -C ₂₀₎ alcohol of the ethylenically unsaturated aliphatic 1,2-dicarboxylic acid diester. Preferably, R ⁹ and R ¹⁰ are H, or R ⁹ and R ¹¹ are H. Accordingly, monomers M3 is preferably maleic anhydride, maleic acid, fumaric acid, C ₁ -C ₂₀ - maleic acid in alcohol mono- and di-esters, and C ₁ -C ₂₀ - and selected from di-ester-alcohol of the fumaric acid monomethyl do. Examples of monomers M3 include, but are not limited to, monomethyl, monoethyl, monopropyl, monoisopropyl, mono-n-butyl, mono-sec-butyl, monoisobutyl, mono-tert- butyl, monopentyl, monohexyl, mono Heptyl, mono-octyl, mono-2-ethylhexyl, monononyl, monodecyl, mono-2-propylheptyl, mono-4-methyl-2-propylhexyl, monoundecyl, monododecyl, Decyl, monopentadecyl, monohexadecyl, monoheptadecyl, monooctadecyl, monononadecyl, monoecosyl fumarate and maleate, and the corresponding fumaric and maleic acid diesters of the corresponding alcohols.

The copolymer of the present invention is not a graft copolymer and is not crosslinked. This may be of straight-chain or branched, where including the short chain branching due to the CH ₂ radical for typically minutes CH ₂ baek-biting (backbiting around the copolymer (for example comonomer units having a branched structure) that is generated from the high pressure polymerization ).

The copolymers of the present invention preferably have a number average molecular weight M _{n in the range} of about 1,000 to 4,800, more preferably 1,500 to 4,500, and most preferably 2,000 to 4,000 g / mol.

The copolymer of the present invention preferably has an M _w / M _n ratio (= PDI) in the range of 1.5 to 5.0, preferably 1.8 to 4.0, particularly 1.9 to 3.5.

Details of the weight-average molecular weight (M _w ) number-average molecular weight (M _n ) and its index PDI (= M _w / M _n ) given in the context of the present invention are preferably determined by gel permeation chromatography (polystyrene standard) Lt; / RTI >

The viscosity of the inventive copolymer (measured according to Ubbelohde DIN 51562) is typically in the range of about 100 to about 3,000 mm ² / s, in particular about 250 to about 2,750 mm ² / s, 500 to about 2,500 mm ² / s.

Preparation of Copolymer

Polymers of the present invention or polymers used in accordance with the present invention for direct free-radical high-pressure copolymerization of unsaturated compounds are prepared by known methods per se, preferably from the prior art (see, for example, Ullmann's A-157486, EP-A-244855, < / RTI > < RTI ID = 0.0 > EP-A-0007590, US 6,300,430, US 3,627,838, DE-A-2515805, DE-A-3141507).

The polymer is prepared in a stirred high-pressure autoclave, more preferably a high-pressure tubular reactor or a combination of the two. In an autoclave, the length / diameter ratio varies mainly from 2: 1 to 30: 1, preferably from 5: 1 to 20: 1. Tubular reactors are predominantly length / diameter ratios> 1,000, preferably from 5,000 to 30,000.

High pressure polymerization is typically carried out under pressure in the range of 1,000 to 3,000 bar, preferably 1,500 to 2,000 bar. Typically, the reaction temperature is in the range of 120 to 320 占 폚, preferably 140 to 280 占 폚, more preferably 140 to 250 占 폚.

The modifier used to control the molecular weight of the copolymer is selected, for example, from aliphatic aldehydes and aliphatic ketones of the formula (I) and mixtures thereof:

[Wherein,

R ^a and R ^b are the same or different and are selected from:

- Hydrogen;

- C ₁ -C ₆ - alkyl, such as methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert- butyl, n- pentyl, isopentyl, sec- pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl; More preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; And

- C ₃ -C ₁₂ -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclodecyl and cyclododecyl; Preferably cyclopentyl, cyclohexyl and cycloheptyl; or

R ^a and R ^b are covalently bonded to each other to form a 4- to 13-membered ring. For example, with R ^a and R ^b is _{- (CH 2) 4 -,} - (CH 2) 5 -, - (CH 2) 6, - (CH 2) 7 -, -CH (CH 3) -CH 2 -CH ₂ -CH (CH ₃ ) - and -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -.

The use of propionaldehyde or ethyl methyl ketone as the modifier is very particularly preferred.

Also highly suitable modifiers are non-branched aliphatic hydrocarbons, such as propane, or branched aliphatic hydrocarbons having tertiary hydrogen atoms, such as isobutane, isopentane, isooctane or isododecane (2,2,4,6, Pentamethylheptane). Further, further adjusting agents such as olefins (e.g., propylene, butane, hexane) may be used.

A mixture of the above-mentioned regulator and hydrogen or hydrogen alone is also preferable.

The amount of regulator (s) used corresponds to the amount customary for high pressure polymerization processes.

The starting materials used for the free-radical polymerization can be conventional free-radical initiators, such as organic peroxides, oxygen or azo compounds. Mixtures of a plurality of free-radical initiators are also suitable. The free-radical initiator used is, for example, one or more peroxides selected from the following commercially available materials:

2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert- butyl (Tert-butylperoxycarbo) cyclohexane (as an isomer mixture), tert-butylperoxydiethyl isobutyrate, tert-butylperoxydiisobutyrate, (Tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, methyl isobutyl ketone peroxide Tert-butyl peroxy isopropyl carbonate, 2,2-di (tert-butylperoxy) butane, tert-butyl peroxyacetate, tert-butyl peroxypivalate or tert-amyl peroxy pivalate;

butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, isomeric di (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl- Butylperoxy hexane, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) Propyl monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide;

- Dimeric or dimeric ketone peroxides (described, for example, in EP 0813550).

Particularly suitable peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisonanoate or tert-butyl peroxy-2-ethylhexanoate or mixtures thereof. An example of an azo compound is azobisisobutyronitrile "AIBN ". The free-radical initiator is quantified in a conventional amount to the polymer.

According to a preferred method, the copolymer of the present invention comprises a tubular reactor maintained at a pressure ranging from about 1,500 to 2,000 bar (e.g., about 1,700 bar) and a temperature ranging from about 120 to 160 占 폚 (A) and (b), if desired, and optionally monomer (s) (c) (e.g. one or more of monomers M1, M2 and M3), individually or as a mixture, preferably continuously . As a result of the continuous addition of an initiator which is generally dissolved in a suitable solvent, for example isododecane, the temperature of the reaction mixture increases. The process conditions (particularly the rate of initiator addition) are adjusted to maintain the temperature in the reactor at the desired reaction temperature, for example, in the range of 200 to 250 ° C. The polymer present in the effluent can be isolated in a conventional manner or recycled to the reactor with the unconverted reactant.

Variations of this method are of course possible and can be practiced by those skilled in the art without unacceptable effort. For example, the monomers and modifiers can be metered separately in the reaction mixture and / or the reaction temperature can be varied, e.g., modified during the process.

The copolymers of the present invention comprise monomeric units derived from monomer (a), monomer (b) and, if present, monomer (c), in essentially random distribution. Nevertheless, due to the different polymerization rates under given polymerization conditions depending on the choice of the individual monomers, a gradient copolymer can be formed. For example, acrylates are often polymerized more rapidly than vinyl acetate under the reaction conditions described above, e.g., the acrylate concentration decreases along the main polymer chain while vinyl acetate and ethylene are essentially uniformly distributed throughout the chain ≪ / RTI >

High pressure polymerization enables the introduction of a large amount of polar monomers into the back bone of polyethylene. Alternatively, intermediate pressure techniques (typically 70-300 bar) can be used for the polymerization, but the solvent is added to the reaction mixture during the polymerization process. The solvent may be, for example, a cosmetic oil. High pressure polymerization is preferred because solvent addition to the monomer solution is not required (excess supercritical ethylene in the reaction mixture can act as a solvent).

The oil solution of the copolymer

The copolymers of the present invention are soluble in oils and are preferably used as additives in oils.

For convenience, the copolymers of the present invention are cosmetically acceptable and are therefore useful as additives for cosmetic formulations (especially liquids). "Cosmetically acceptable" means that each compound does not cause unwanted reactions, such as skin irritation when used in cosmetic formulations.

Preferably the copolymer is used as an additive in natural oils used in cosmetic formulations, such as vegetable oils, i.e. fatty acid esters which are naturally occurring in plants (typically oily fruits thereof) (generally in the form of triglycerides) . Virtually all vegetable oils are suitable for cosmetic applications, and soybean oil, rapeseed oil and palm oil are most commonly used. Other vegetable oils commonly used in cosmetics include argan oil, avocado oil, rose oil, sunflower oil, olive oil and coconut oil.

The oil solution of the inventive copolymer can be stable at room temperature (or higher temperature) for at least 1 h, and stable for longer than 24 h at room temperature. The stable copolymer / oil solution remains homogeneous and clear without any phase separation, particle formation, visible turbidity, over a specified period of time (e.g., greater than 1 h or even greater than 24 h at room temperature).

Natural oils generally contain alkyl chains and polar groups. Without being bound by theory, the presence of (meth) acrylate-derived monomeric units in a copolymer consisting primarily of monomeric units derived from ethylene reduces the crystallinity of the copolymer and results in monomeric units derived from propylheptyl (meth) The presence of a branched side chain of units increases the solubility of the copolymer in the oil and provides a molecular interaction that is strong enough to allow the solution of the copolymer of the present invention in the oil to remain stable for at least 1 h at room temperature .

Uses of Copolymers in Cosmetic Formulations

The copolymer / oil solution described herein can be used in cosmetic formulations. This is particularly useful as an additive for liquid cosmetic formulations, preferably for rinse-off cosmetic formulations, such as body wash, shampoo and conditioner formulations. In such applications, the copolymers of the present invention serve to increase the amount of oil left on the skin or hair after rinsing. In other words, the copolymer of the present invention can act as an oil deposition improver.

Liquid cosmetic formulations, such as body wash and shampoo formulations, with the oil solutions described herein can be prepared by mixing the premixed copolymer / oil solution in a ratio of, for example, about 10 parts by weight copolymer / oil solution to about 90 parts by weight base formulation Liquid base formulation (e. G., Body wash or shampoo formulation).

Typically, oil-replenishing liquid cosmetic formulations (such as body wash or shampoo formulations) containing a copolymer of the present invention (added as a pre-mix with an oil) may be at least 1 month, at least 3 months, or even 6 months and more Gt; 10-50 < / RTI >

The copolymers of the present invention can also be used alone or in combination with conventional additives having oil deposition improving properties.

The copolymers of the present invention are conveniently used in quantitative proportions based on the total amount of the oil solution, which exhibit essentially sufficient oil deposition improvement effects in the final formulation. For example, the copolymer may be present in an amount of 0.01 to 10.00 wt-%, preferably 0.05 to 6.00 wt-%, more preferably 0.1 to 3.0 wt-%, specifically 0.5 to 1.5 wt-%, based on the total weight of the formulation. . ≪ / RTI >

Example

1) Preparation of polymer

A total of 19 different polymers were prepared by high pressure polymerization of the corresponding monomers at reaction temperatures of 210 ° C to 240 ° C and pressures of 1,600 to 1,800 bar. Their amounts in the total weight of the monomers and the resulting polymer are shown in Table 1.

The viscosity, number-average molecular weight and PDI (= M _w / M _n ) of the polymer were measured (see Table 1). High temperature gel permeation chromatography using the method described in ISO 16014-1: 2003 (E) and ISO 16014-4: 2003 (E), solvent 1,2,4-trichlorobenzene (TCB) Average molecular weight (M _n ) and weight-average molecular weight (M _w ) by means of a PolymerChar IR-4 infrared detector (suitable for use with TCB) as a temperature detector and a concentration detector. A monodisperse polystyrene (PS) standard ranging from 580 g / mol to 11,600,000 g / mol or less was used for molecular weight calibration. The resulting calibration curve was fitted to polyethylene (PE) by the universal calibration method according to ISO 16014-2: 2003 (E). The viscosity was measured according to Ubbelohde DIN 51562 at 120 캜.

In addition, the monomer content of the resulting polymer was determined by < 1 > H-NMR spectroscopy (data not shown) using a Bruker AV 501 instrument (tetrachloroethane, 373K). The monomer content was less than 1,000 ppm in each case.

Table 1

Abbreviations of monomers:

E = ethylene EHA = ethylhexyl acrylate

PHA = 2-propylheptyl acrylate SA = stearyl acrylate

PHMA = 2-propylheptyl methacrylate VAC = vinyl acetate

2) Oil solution

A mixture of 10 wt-% polymer in soybean oil was prepared and heated slowly under shaking. In each example, the minimum temperature at which a homogeneous, clear solution was formed without any phase separation, particle formation or visible turbidity (see "Min. Solution temperature in SBO" in Table 2).

The stability of the 10 wt-% polymer / oil solution was also monitored at room temperature (see "Stability of SBO solution" in Table 2). The solutions were considered stable as long as they remained homogeneous without any visible phase separation.

3) Cosmetic formulations

The premixed oil of Example 2 (pre-heated at a temperature above the respective minimum dissolution temperature) was added to a liquid body wash base formulation (composition given in Table 2) in a weight ratio of 10 parts oil solution to 90 parts base formulation, Or liquid shampoo base formulations (compositions shown in Table 3) (each preheated to 80 캜).

Table 2

Table 3

The oil-replenishing liquid formulations were stored at 25 占 폚 and their stability was monitored (see "Stability of Body Wash" and "Stability of Shampoo" in Table 4). The formulations were considered stable so long as they remained homogeneous without any visible phase separation or large lump formation visible.

In addition, the oil deposition effect was evaluated using the above-mentioned body wash formulation. The tester applied a defined amount of body wash formulation to his / her hands, rinsed the formulation with water, and then rated the oil deposition by the feel evaluation (where "x" is the perceptible oil on the treated hands Quot; xx "represents a perceptible oil deposition to moderate levels, and" xxx " represents a strongly perceivable oil deposition) (see "Oil Deposition" in Table 4).

Table 4

The exemplary copolymers of the present invention 1-11 exhibited relatively low minimum dissolution temperatures when mixed with soybean oil and formed an oil solution with high stability (> 24 h). In addition, the copolymers of Examples 1-11 had a significant oil deposition effect in all cases except when significant and one was used when used in rinse-off body wash formulations. The oil deposition effects of Reference Examples A, B and H were also significant to strong. However, the oil solution and cosmetic formulation were significantly less stable, and the minimum dissolution temperature in the soybean oil was significantly higher than in the case of Examples 1-11. Other reference examples did not show any significant oil deposition effect and in all cases also showed poor stability of the respective oil solutions and cosmetic formulations.

Claims (9)

Copolymers formed from the following monomers:
(a) ethylene,
(b) at least one monomer selected from propylheptyl acrylate, propylheptyl methacrylate and mixtures thereof, and
(c) optionally one or more additional monomers different from (a) and (b)
here,
(i) the amount of ethylene monomer (a) is in the range of 75 wt-% to 98 wt-%, based on the total weight of the monomers forming the copolymer;
(ii) the total amount of monomers (a) + (b) is at least 90 wt-% based on the total weight of the monomers forming the copolymer;
(iii) when present, the amount by weight of the monomer (s) (c) is less than the amount by weight of the monomer (s) (b). The copolymer according to claim 1, wherein the total amount of the monomers (a) + (b) is 95 wt% or more based on the total weight of the monomers forming the copolymer. The copolymer of claim 1, formed from only monomers (a) and (b). The copolymer according to any one of claims 1 to 3, wherein the amount of the ethylene monomer (a) ranges from 78 wt% to 97 wt% with respect to the total weight of the monomers forming the copolymer. The copolymer according to any one of claims 1 to 4, wherein the monomer (b) is propylheptyl acrylate. The copolymer according to claim 5, wherein the monomer (b) is 2-propylheptyl acrylate. The copolymer according to any one of claims 1, 2 and 4 to 6, wherein the monomer (s) (c) is selected from the monomers of the formula (M1)

[Wherein,
R ¹ , R ² and R ³ are each independently H or C ₁ -C ₄ -alkyl;
R ⁴ is C ₁ -C ₂₀ - alkyl. The copolymer according to claim 7, wherein the monomer (c) is vinyl acetate. Any one of claims 1 to A method according to any one of claim 8, wherein the number-average molecular weight M _n of 1,000 to 4,800 g / mol range of copolymers.